TW202323496A - Heterocyclic compound and organic light emitting device using same - Google Patents

Abstract

Disclosed are a heterocyclic compound which may significantly improve a service life, efficiency, electrochemical stability, and thermal stability of an organic light emitting device, and an organic light emitting device in which the heterocyclic compound is contained in an organic material layer.

Description

Heterocyclic compound and organic light-emitting device using same

Cross References to Related Applications

This application claims priority and benefit from Korean Patent Application No. 10-2021-0112426 filed with the Korean Intellectual Property Office on Aug. 25, 2021, the entire contents of which are incorporated herein by reference.

The present application relates to a heterocyclic compound and an organic light-emitting device using the same.

The electroluminescent device is a self-emissive display device, and has the advantages of wide viewing angle, excellent contrast ratio and fast response speed.

An organic light emitting device has a structure in which an organic thin film is disposed between two electrodes. When a voltage is applied to the organic light emitting device having the structure, electrons and holes injected from two electrodes combine with each other in the organic thin film to form a pair, and then emit light when turned off. The organic thin film may consist of a single layer or multiple layers, as desired.

The material of the organic thin film may have a light-emitting function as needed. For example, as the material of the organic thin film, it is also possible to use a compound that can constitute a light-emitting layer by itself, or a compound that can serve as a host or a dopant for a host-dopant-based light-emitting layer. Furthermore, as a material of the organic thin film, it is also possible to use a compound that can perform functions such as hole injection, hole transport, electron blocking, hole blocking, electron transport, or electron injection.

In order to improve the performance, lifetime, or efficiency of organic light-emitting devices, there is a continuing need to develop materials for organic thin films.

[Prior Art Document]

[Patent Document]

US Patent No. 4,356,429

The present specification has been devoted to providing a heterocyclic compound and an organic light-emitting device comprising the same.

在化學式1中， L1和L2彼此相同或不同，且各自獨立地為直接鍵、具有6個到60個碳原子的經取代或未經取代的伸芳基或具有2個到60個碳原子的經取代或未經取代的雜伸芳基，a和b各自為0到3的整數，在a為2或高於2時，括弧中的L1彼此相同或不同，且在b為2或高於2時，括弧中的L2彼此相同或不同， R1和R2中的一個為經取代或未經取代的胺基，且另一個為未經取代或經由氘、具有1個到10個碳原子的烷基以及具有6個到20個碳原子的芳基所組成的群組中選出的一或多個取代基取代的芴基；經取代或未經取代的芘基；具有21個到60個碳原子的經取代或未經取代的芳基；或具有2個到60個碳原子的經取代或未經取代的雜芳基， X1和X2各自獨立地為氫、氘、鹵素基團、具有1個到60個碳原子的經取代或未經取代的烷基、具有3個到60個碳原子的經取代或未經取代的環烷基、具有6個到60個碳原子的經取代或未經取代的芳基或具有2個到60個碳原子的經取代或未經取代的雜環基， m為0到3的整數，且在m為2或高於2時，括弧中的X1彼此相同或不同，且 n為0到5的整數，且在n為2或高於2時，括弧中的X2彼此相同或不同。 Exemplary embodiments of the present application provide a heterocyclic compound represented by Chemical Formula 1 below. [chemical formula 1]

In Chemical Formula 1, L1 and L2 are the same or different from each other, and are each independently a direct bond, a substituted or unsubstituted arylylene group having 6 to 60 carbon atoms, or a group having 2 to 60 carbon atoms Substituted or unsubstituted heteroaryl, a and b are each an integer from 0 to 3, when a is 2 or higher than 2, L1 in the brackets are the same or different from each other, and when b is 2 or higher 2, L2 in the brackets are the same or different from each other, one of R1 and R2 is a substituted or unsubstituted amino group, and the other is an unsubstituted or via deuterium, an alkane having 1 to 10 carbon atoms Fluorenyl substituted with one or more substituents selected from the group consisting of aryl and aryl having 6 to 20 carbon atoms; substituted or unsubstituted pyrenyl; having 21 to 60 carbon atoms substituted or unsubstituted aryl; or substituted or unsubstituted heteroaryl having 2 to 60 carbon atoms, X1 and X2 are each independently hydrogen, deuterium, halogen group, with 1 Substituted or unsubstituted alkyl groups of up to 60 carbon atoms, substituted or unsubstituted cycloalkyl groups of 3 to 60 carbon atoms, substituted or unsubstituted cycloalkyl groups of 6 to 60 carbon atoms A substituted aryl group or a substituted or unsubstituted heterocyclic group having 2 to 60 carbon atoms, m is an integer of 0 to 3, and when m is 2 or higher, X1 in parentheses are the same as each other or different, and n is an integer from 0 to 5, and when n is 2 or higher than 2, X2 in parentheses are the same or different from each other.

In addition, another exemplary embodiment of the present application provides an organic light emitting device including a first electrode, a second electrode, and one or more layers disposed between the first electrode and the second electrode. wherein one or more layers of the organic material layer includes the heterocyclic compound represented by Chemical Formula 1.

The heterocyclic compound according to an exemplary embodiment of the present application may be used as a material of an organic material layer of an organic light emitting device. Heterocyclic compounds are useful as materials for hole injection layers, hole transport layers, light emitting layers, electron transport layers, electron injection layers, charge generation layers, and the like in organic light emitting devices. Specifically, the heterocyclic compound represented by Chemical Formula 1 may be used as a material of a hole transport layer or a hole transport auxiliary layer of an organic light emitting device. In addition, when the heterocyclic compound represented by Chemical Formula 1 is used in an organic light emitting device, the driving voltage of the device may be reduced, the light efficiency of the device may be improved, and the lifetime characteristics of the device may be improved due to the thermal stability of the compound.

Hereinafter, the present application will be described in detail.

在化學式1中， L1和L2彼此相同或不同，且各自獨立地為直接鍵、具有6個到60個碳原子的經取代或未經取代的伸芳基或具有2個到60個碳原子的經取代或未經取代的雜伸芳基，a和b各自為0到3的整數，在a為2或高於2時，括弧中的L1彼此相同或不同，且在b為2或高於2時，括弧中的L2彼此相同或不同， R1和R2中的一個為經取代或未經取代的胺基，且另一個為未經取代或經由氘、具有1個到10個碳原子的烷基以及具有6個到20個碳原子的芳基所組成的群組中選出的一或多個取代基取代的芴基；經取代或未經取代的芘基；具有21個到60個碳原子的經取代或未經取代的芳基；或具有2個到60個碳原子的經取代或未經取代的雜芳基， X1和X2各自獨立地為氫、氘、鹵素基團、具有1個到60個碳原子的經取代或未經取代的烷基、具有3個到60個碳原子的經取代或未經取代的環烷基、具有6個到60個碳原子的經取代或未經取代的芳基或具有2個到60個碳原子的經取代或未經取代的雜環基， m為0到3的整數，且在m為2或高於2時，括弧中的X1彼此相同或不同，且 n為0到5的整數，且在n為2或高於2時，括弧中的X2彼此相同或不同。 Exemplary embodiments of the present application provide a heterocyclic compound represented by Chemical Formula 1 below. [chemical formula 1]

In Chemical Formula 1, L1 and L2 are the same or different from each other, and are each independently a direct bond, a substituted or unsubstituted arylylene group having 6 to 60 carbon atoms, or a group having 2 to 60 carbon atoms Substituted or unsubstituted heteroaryl, a and b are each an integer from 0 to 3, when a is 2 or higher than 2, L1 in the brackets are the same or different from each other, and when b is 2 or higher 2, L2 in the brackets are the same or different from each other, one of R1 and R2 is a substituted or unsubstituted amino group, and the other is an unsubstituted or via deuterium, an alkane having 1 to 10 carbon atoms Fluorenyl substituted with one or more substituents selected from the group consisting of aryl and aryl having 6 to 20 carbon atoms; substituted or unsubstituted pyrenyl; having 21 to 60 carbon atoms substituted or unsubstituted aryl; or substituted or unsubstituted heteroaryl having 2 to 60 carbon atoms, X1 and X2 are each independently hydrogen, deuterium, halogen group, with 1 Substituted or unsubstituted alkyl groups of up to 60 carbon atoms, substituted or unsubstituted cycloalkyl groups of 3 to 60 carbon atoms, substituted or unsubstituted cycloalkyl groups of 6 to 60 carbon atoms A substituted aryl group or a substituted or unsubstituted heterocyclic group having 2 to 60 carbon atoms, m is an integer of 0 to 3, and when m is 2 or higher, X1 in parentheses are the same as each other or different, and n is an integer from 0 to 5, and when n is 2 or higher than 2, X2 in parentheses are the same or different from each other.

The heterocyclic compound represented by Chemical Formula 1 may have a structure in which two specific substituents including amine groups in naphthobenzofuran are substituted to delocalize the highest occupied molecular orbital (HOMO) energy level , thereby increasing the hole transport capability and stabilizing the HOMO energy.

In addition, the planarity and glass transition temperature of the amine derivatives can be increased to enhance the thermal stability of the compound by bonding the amine moiety to a substituent with enhanced hole characteristics. In addition, the heterocyclic compound represented by Chemical Formula 1 has a structure in which only one amine group is substituted, the molecular weight is lower than the case where two amine groups are substituted or the amine group is not used as a substituent, and can be formed for hole injection and transport. Appropriate HOMO for , and thermal stability can be achieved by allowing the material to have a spatial structure.

In addition, the heterocyclic compound represented by Chemical Formula 1 may improve hole transfer ability, and may also enhance stability of molecules by adjusting a band gap and a Ti value (energy level value of a triplet state).

Furthermore, since substituents other than amine correspond to specific substituents or aryl groups with specific carbon numbers, it is possible to form HOMOs in which holes are more easily injected and transported than with other substituents.

Due to the characteristics, when the material of Chemical Formula 1 is used as a material of a hole transport layer in an organic light emitting device, a driving voltage of the device may be reduced and luminous efficiency of the device may be improved. In addition, when the heterocyclic compound represented by Chemical Formula 1 is used as a material of the hole transport auxiliary layer, transfer of electrons from the opposite side of the electron transport layer may be effectively prevented, thereby improving the efficiency of the device.

In addition, the service life of the device using the heterocyclic compound represented by Chemical Formula 1 may be improved by the thermal stability of the heterocyclic compound represented by Chemical Formula 1.

In this specification, the term "substitution" means that a hydrogen atom bonded to a carbon atom of a compound becomes another substituent, and the position to be substituted is not limited as long as the position is a position where a hydrogen atom is substituted, that is, the substituent can be In the substituted position, and when two or more substituents are substituted, the two or more substituents may be the same or different from each other.

In this specification, "substituted or unsubstituted" means unsubstituted or substituted by one or more substituents selected from the group consisting of deuterium, cyano, halogen, with 1 Straight chain or branched chain alkyl with 2 to 60 carbon atoms, straight chain or branched chain alkenyl with 2 to 60 carbon atoms, straight chain or branched chain alkynyl with 2 to 60 carbon atoms, with 3 Monocyclic or polycyclic cycloalkyl groups having 2 to 60 carbon atoms, monocyclic or polycyclic heterocycloalkyl groups having 2 to 60 carbon atoms, monocyclic or polycyclic aromatic groups having 6 to 60 carbon atoms group, monocyclic or polycyclic heteroaryl group with 2 to 60 carbon atoms, -SiRR'R", -P(=O)RR', alkylamine with 1 to 20 carbon atoms, with 6 Monocyclic or polycyclic arylamines with 2 to 60 carbon atoms and monocyclic or polycyclic heteroarylamines with 2 to 60 carbon atoms, or unsubstituted or via two selected from the above exemplary substituents One or more substituents to which two substituents are bonded are substituted, and mean that R, R' and R" are the same or different from each other, and are each independently substituted or unsubstituted with 1 to 60 carbon atoms Alkyl, substituted or unsubstituted aryl having 6 to 60 carbon atoms, or substituted or unsubstituted heteroaryl having 2 to 60 carbon atoms.

In the present specification, "when no substituent is indicated in the chemical formula or the structure of the compound" means that a hydrogen atom is bonded to a carbon atom. However, since deuterium ( ² H) is an isotope of hydrogen, some hydrogen atoms may be deuterium.

In an exemplary embodiment of the present application, "when no substituent is indicated in the chemical formula or the structure of the compound" may mean that all positions accessible by the substituent are hydrogen or deuterium. That is, deuterium is an isotope of hydrogen, and some hydrogen atoms may be deuterium as an isotope, and in this case, the content of deuterium may be 0% to 100%.

In the exemplary embodiment of the present application, in "the case where no substituent is indicated in the chemical formula or the structure of the compound", when the content of deuterium is 0%, the content of hydrogen is 100%, and all the substituents are not Deuterium, such as hydrogen, is expressly excluded, and hydrogen and deuterium may be mixed and used in compounds.

In the exemplary embodiment of the present application, deuterium is one of the isotopes of hydrogen, is an element having a deuteron composed of one proton and one neutron as an atomic nucleus, and can be represented by hydrogen-2, and the element symbol can also be Expressed as D or 2H.

In the exemplary embodiments of the present application, isotopes mean atoms having the same atomic number (Z) but different mass numbers (A), and isotopes can be interpreted as those having the same number of protons but different numbers of neutrons element.

In an exemplary embodiment of the present application, when the total number of substituents of the basic compound is defined as T1 and the number of specific substituents among the substituents is defined as T2, the content T% of the specific substituent can be defined as T2 /T1×100 = T%.

表示的苯基中的20%的氘含量可由20%表示。也就是說，苯基中的20%的氘含量可由以下結構式表示。

That is, in the example, when the total number of substituents that phenyl may have is 5 (T1 in the formula) and the number of deuterium among the substituents is 1 (T2 in the formula), by

A deuterium content of 20% in the indicated phenyl group can be represented by 20%. That is, the 20% deuterium content in the phenyl group can be represented by the following structural formula.

In addition, in an exemplary embodiment of the present application, "a phenyl group having a deuterium content of 0%" may mean a phenyl group not including a deuterium atom, ie, a phenyl group having five hydrogen atoms.

In this specification, halogen may be fluorine, chlorine, bromine or iodine.

In the present specification, the alkyl group includes straight or branched chains having 1 to 60 carbon atoms, and may be additionally substituted with another substituent. The number of carbon atoms of the alkyl group may be 1 to 60, specifically 1 to 40, and more specifically 1 to 20. Specific examples thereof include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1- Ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2 -Pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl Base, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1, 1-Dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl and the like, but not limited thereto.

In the present specification, the alkenyl group includes a straight or branched chain having 2 to 60 carbon atoms, and may be additionally substituted with another substituent. The number of carbon atoms of the alkenyl group may be 2 to 60, specifically 2 to 40, and more specifically 2 to 20. Specific examples thereof include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl Base, 3-methyl-1-butenyl, 1,3-butadienyl, allyl, 1-phenylethenyl-1-yl, 2-phenylethenyl-1-yl, 2, 2-Diphenylethenyl-1-yl, 2-phenyl-2-(naphthyl-1-yl)ethenyl-1-yl, 2,2-bis(diphenyl-1-yl)ethenyl -1-yl, stilbenyl group, styryl group and the like, but not limited thereto.

In the present specification, the alkynyl group includes a straight or branched chain having 2 to 60 carbon atoms, and may be additionally substituted with another substituent. The number of carbon atoms of the alkynyl group may be 2 to 60, specifically 2 to 40, and more specifically 2 to 20.

In this specification, an alkoxy group may be linear, branched or cyclic. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 20. Specific examples thereof include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, t-butoxy, sec-butoxy, n-pentoxy, neopentyloxy Base, isopentyloxy, n-hexyloxy, 3,3-dimethylbutoxy, 2-ethylbutoxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, para Methylbenzyloxy and the like, but not limited thereto.

In the present specification, the cycloalkyl group includes a monocyclic or polycyclic ring having 3 to 60 carbon atoms, and may be additionally substituted with another substituent. Here, polycyclic means a group in which a cycloalkyl group is directly bonded to or fused to another cyclic group. Here, the other cyclic group may also be a cycloalkyl group, but may also be another kind of cyclic group such as a heterocycloalkyl group, an aryl group, a heteroaryl group, and the like. The number of carbon atoms of the cycloalkyl group may be 3 to 60, specifically 3 to 40, and more specifically 5 to 20. Specific examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclopentyl, Hexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl and the like, but not limited thereto.

In the present specification, the heterocycloalkyl group contains O, S, Se, N or Si as a hetero atom, contains a monocyclic or polycyclic ring having 2 to 60 carbon atoms, and may be additionally substituted with another substituent. Here, polycyclic means a group in which a heterocycloalkyl group is directly bonded to or fused to another cyclic group. Here, the other cyclic group may also be a heterocycloalkyl group, but may also be another kind of cyclic group such as a cycloalkyl group, an aryl group, a heteroaryl group, and the like. The number of carbon atoms of the heterocycloalkyl group may be 2 to 60, specifically 2 to 40, and more specifically 3 to 20.

In the present specification, the aryl group includes a monocyclic or polycyclic ring having 6 to 60 carbon atoms, and may be additionally substituted with another substituent. Here, polycyclic means a group in which an aryl group is directly bonded to or fused to another cyclic group. Here, the other cyclic group may also be an aryl group, but may also be another kind of cyclic group such as cycloalkyl, heterocycloalkyl, heteroaryl and the like. Aryl groups contain spiro groups. The number of carbon atoms of the aryl group may be 6 to 60, specifically 6 to 40, and more specifically 6 to 25. Specific examples of aryl groups include phenyl, biphenyl, triphenyl, naphthyl, anthracenyl, chrysyl, phenanthrenyl, perylene, fluoranthenyl group, triphenylene, phenalenyl group), pyrenyl, tetracenyl group, pentacenyl group, fluorenyl, indenyl, acenaphthyl, benzofluorenyl, spirobifluorenyl group, 2,3 - Dihydro-1H-indenyl, fused cyclic groups thereof and the like, but not limited thereto.

In this specification, the phosphine oxide group is represented by -P(=O)R101R102, and R101 and R102 are the same or different from each other, and each independently may be a substituent composed of at least one of the following: hydrogen, deuterium, halogen group group, alkyl, alkenyl, alkoxy, cycloalkyl, aryl and heterocyclyl. Specific examples of the phosphine oxide group include diphenylphosphine oxide, dinaphthylphosphine oxide, and the like, but are not limited thereto.

In this specification, the silyl group (silyl group) contains Si and is a substituent to which a Si atom is directly bonded as a free radical, and is represented by -SiR104R105R106, and R104 to R106 are the same or different from each other, and can be each independently represented by A substituent composed of at least one of the following: hydrogen, deuterium, halogen group, alkyl, alkenyl, alkoxy, cycloalkyl, aryl and heterocyclic group. Specific examples of silyl groups include trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, vinyldimethylsilyl, propyldimethylsilyl, triphenylsilyl, di Phenylsilyl, phenylsilyl and the like, but not limited thereto.

In this specification, the fluorenyl group may be substituted, and adjacent substituents may be bonded to each other to form a ring.

In the present specification, a spiro group is a group including a spiro structure, and may have 15 to 60 carbon atoms. For example, a spiro group may comprise a structure in which a 2,3-dihydro-1H-indenyl or cyclohexyl group is spiro-bonded to a fluorenyl group. Specifically, the spiro group may comprise any one of the groups of the following structural formulae.

In the present specification, the heteroaryl group contains S, O, Se, N or Si as a heteroatom, contains a monocyclic or polycyclic ring having 2 to 60 carbon atoms, and may be additionally substituted with another substituent. Here, polycyclic means a group in which a heteroaryl group is directly bonded to another cyclic group or fused with another cyclic group. Here, the other cyclic group may also be a heteroaryl group, but may also be another kind of cyclic group such as cycloalkyl, heterocycloalkyl, aryl and the like. The number of carbon atoms in the heteroaryl group can be 2 to 60, specifically 2 to 40, and more specifically 3 to 25. Specific examples of heteroaryl include pyridyl, pyrrolyl, pyrimidinyl, pyridazinyl, furyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, tri Azolyl, furanyl, oxadiazolyl, thiadiazolyl, bithiazolyl, tetrazolyl, pyranyl, thiopyranyl, diazinyl, oxazinyl, thiazinyl, dioxy (dioxynyl group), triazinyl, tetrazinyl, quinolinyl, isoquinolyl, quinazolinyl, isoquinazolinyl, quinozolilyl group, naphthyridinyl, acridinyl, Phenanthridine, imidazopyridyl, naphthyl, triazindenyl, indolyl, indolazinyl, benzothiazolyl, benzoxazolyl, benzimidazolyl, benzothienyl , benzofuryl, dibenzothienyl, dibenzofuryl, carbazolyl, benzocarbazolyl, dibenzocarbazolyl, phenazinyl, dibenzosilole group, Spirobis(dibenzosilole), dihydrophenazinyl, phenoxazinyl, phenanthridyl group, imidazopyridyl, thienyl, indolo[2,3-a]carbazolyl , Indolo[2,3-b]carbazolyl, indolinyl, 10,11-dihydro-dibenzo[b,f]azepine, 9,10-dihydroacridinyl, phen Phenanthrazinyl (phenanthrazinyl group), phenothiazinyl, phenanthrazinyl, naphthyridinyl, phenanthrolinyl, benzo[c][1,2,5]thiadiazolyl, 5,10-dihydrodi Benzo[b,e][1,4]azasilyl, pyrazolo[1,5-c]quinazolinyl, pyrido[1,2-b]indazolyl, pyrido[1, 2-a]imidazo[1,2-e]indolinyl, 5,11-dihydroindeno[1,2-b]carbazolyl and the like, but not limited thereto.

In this specification, the amine group can be selected from the group consisting of: monoalkylamine group, monoarylamine group, monoheteroarylamine group, -NH ₂ , dialkylamine group, dialkylamine group, Arylamine groups, diheteroarylamine groups, alkylarylamine groups, alkylheteroarylamine groups, and arylheteroarylamine groups, and the number of carbon atoms thereof is not particularly limited, But preferably 1 to 30. Specific examples of amine groups include methylamine groups, dimethylamine groups, ethylamine groups, diethylamine groups, aniline groups, naphthylamine groups, benzidine groups, dibenzidine groups, anthramine groups, group, 9-methyl-anthraceneamine group, diphenylamine group, phenylnaphthylamine group, xylidine group, phenyltoluidine group, triphenylamine group, biphenylnaphthylamine group , phenyl benzidine group, biphenyl fluorenamine group, phenyl trianilide group, biphenyl trianilide group and the like, but not limited thereto.

In this specification, the aryl group means that there are two bonding positions in the aryl group, that is, a divalent group. The above description for the aryl group is applicable to the arylylene groups except that the arylylene groups are each divalent groups. In addition, heteroaryl means that there are two bonding positions in the heteroaryl group, ie, a divalent group. The above description for heteroaryl is applicable to heteroarylylene, except for divalent heteroarylylene.

In this specification, an "adjacent" group may mean a substituent substituted by an atom directly bonded to the atom on which the corresponding substituent is substituted, a substituent positioned spatially closest to the corresponding substituent, or a substituent substituted by the corresponding substituent. Another substituent substituted by a substituted atom. For example, two substituents substituted at ortho positions in a benzene ring and two substituents substituted by the same carbon in an aliphatic ring may be construed as groups that are "adjacent" to each other.

A heterocyclic compound according to an exemplary embodiment of the present application is represented by Chemical Formula 1. More specifically, the heterocyclic compound represented by Chemical Formula 1 may be used as a material of an organic material layer of an organic light emitting device through structural characteristics of a core structure and substituents as described above.

In an exemplary embodiment of the present application, L1 and L2 of Chemical Formula 1 are the same or different from each other, and are each independently a direct bond, a substituted or unsubstituted aryl or a substituted or unsubstituted hetero Aryl.

In an exemplary embodiment of the present application, L1 and L2 are the same or different from each other, and may each independently be a direct bond, a substituted or unsubstituted arylene group having 6 to 60 carbon atoms, or a arylene group having 2 A substituted or unsubstituted heteroarylylene group of 1 to 60 carbon atoms.

In an exemplary embodiment of the present application, L1 and L2 are the same or different from each other, and may each independently be a direct bond, a substituted or unsubstituted arylene group having 6 to 40 carbon atoms, or a arylene group having 2 A substituted or unsubstituted heteroarylylene group of 1 to 40 carbon atoms.

In an exemplary embodiment of the present application, L1 and L2 are the same or different from each other, and may each independently be a direct bond, a substituted or unsubstituted arylylene group having 6 to 20 carbon atoms, or a arylene group having 2 A substituted or unsubstituted heteroarylylene group of 1 to 20 carbon atoms.

In an exemplary embodiment of the present application, L1 and L2 are the same or different from each other, and are each independently a direct bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, Substituted or unsubstituted naphthylene, substituted or unsubstituted dibenzofuryl or substituted or unsubstituted dibenzothienyl.

In an exemplary embodiment of the present application, L1 and L2 are the same or different from each other, and are each independently a direct bond, phenylene, biphenylene, naphthyl, dibenzofuryl or dibenzothiophene base.

In an exemplary embodiment of the present application, a is 0. In an exemplary embodiment of the present application, a is 1. In an exemplary embodiment of the present application, a is 2. In an exemplary embodiment of the present application, a is 3.

In an exemplary embodiment of the present application, b is 0. In an exemplary embodiment of the present application, b is 1. In an exemplary embodiment of the present application, b is 2. In an exemplary embodiment of the present application, b is 3.

In an exemplary embodiment of the present application, when a is 2 or higher, L1 in parentheses are the same or different from each other.

In an exemplary embodiment of the present application, when b is 2 or higher, L2 in parentheses are the same or different from each other.

In an exemplary embodiment of the present application, one of R1 and R2 of Chemical Formula 1 is a substituted or unsubstituted amino group, and the other may be unsubstituted or via deuterium, having 1 to 10 carbons fluorenyl substituted with one or more substituents selected from the group consisting of alkyl and aryl having 6 to 20 carbon atoms; substituted or unsubstituted pyrenyl; having 21 to 60 a substituted or unsubstituted aryl group having 2 to 60 carbon atoms; or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.

In an exemplary embodiment of the present application, one of R1 and R2 of Chemical Formula 1 is a substituted or unsubstituted amino group, and the other may be unsubstituted or via deuterium, having 1 to 10 carbons Atomic alkyl and fluorenyl substituted with one or more substituents selected from the group consisting of aryl having 6 to 20 carbon atoms; pyrenyl unsubstituted or substituted with one or more deuteriums; A substituted or unsubstituted aryl group having 21 to 60 carbon atoms; or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.

In an exemplary embodiment of the present application, one of R1 and R2 is unsubstituted or substituted or unsubstituted aryl group having 6 to 40 carbon atoms and aryl group having 2 to 40 carbon atoms Amino group substituted with one or more substituents selected from the group consisting of substituted or unsubstituted heteroaryl, and the other may be unsubstituted or via deuterium, having 1 to 10 carbon atoms fluorenyl substituted with one or more substituents selected from the group consisting of alkyl and aryl having 6 to 20 carbon atoms; unsubstituted or substituted pyrenyl with one or more deuteriums; having A substituted or unsubstituted aryl group of 21 to 60 carbon atoms; or a substituted or unsubstituted heteroaryl group of 2 to 60 carbon atoms.

In an exemplary embodiment of the present application, one of R1 and R2 is unsubstituted or substituted or unsubstituted aryl group having 6 to 40 carbon atoms and aryl group having 2 to 40 carbon atoms Amine substituted with one or more substituents selected from the group consisting of substituted or unsubstituted heteroaryl, and the other may be unsubstituted or via deuterium, methyl, and phenyl Fluorenyl substituted with one or more substituents selected from the group; pyrenyl unsubstituted or substituted with one or more deuteriums; substituted or unsubstituted aryl having 21 to 40 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 40 carbon atoms.

In an exemplary embodiment of the present application, one of R1 and R2 is unsubstituted or substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted Naphthyl and substituted or unsubstituted dimethylfluorenyl substituted with one or more substituents selected from the group consisting of amine, and the other can be unsubstituted or via deuterium, substituted or Fluorenyl substituted with one or more substituents selected from the group consisting of unsubstituted methyl and substituted or unsubstituted phenyl; unsubstituted or substituted pyrenyl with one or more deuteriums; A substituted or unsubstituted aryl group having 21 to 60 carbon atoms; a substituted or unsubstituted dibenzofuryl group; a substituted or unsubstituted dibenzothienyl group; or a substituted or unsubstituted Substituted carbazolyl.

In an exemplary embodiment of the present application, R1 is a substituted or unsubstituted amino group, and R2 can be unsubstituted or deuterium, an alkyl group having 1 to 10 carbon atoms, and an alkyl group having 6 to 10 carbon atoms Fluorenyl substituted with one or more substituents selected from the group consisting of aryl having 20 carbon atoms; substituted or unsubstituted pyrenyl; substituted or unsubstituted pyrenyl having 21 to 60 carbon atoms substituted aryl; or substituted or unsubstituted heteroaryl having 2 to 60 carbon atoms.

In an exemplary embodiment of the present application, R2 is a substituted or unsubstituted amino group, and R1 can be unsubstituted or via an alkyl group having 1 to 10 carbon atoms and having 6 to 20 carbon atoms Fluorenyl substituted with one or more substituents selected from the group consisting of aryl of carbon atoms; pyrenyl unsubstituted or substituted with one or more deuteriums; substituted fluorenyl having 21 to 60 carbon atoms or unsubstituted aryl; or substituted or unsubstituted heteroaryl having 2 to 60 carbon atoms.

When one of R1 and R2 of Chemical Formula 1 has a double-substituted structure with an amine group, the highest occupied molecular orbital (HOMO) energy level may be delocalized to increase hole transport capability and stabilize the HOMO energy. This has the effect of forming an appropriate energy level and bandgap with the host material, and thus, increases the drive voltage and efficiency of the device by increasing excitons in the light emitting region.

In an exemplary embodiment of the present application, R1 is a substituted or unsubstituted amino group, and R2 may be a substituted or unsubstituted aryl group having 21 to 60 carbon atoms or having 2 to 60 carbon atoms A substituted or unsubstituted heteroaryl group of 60 carbon atoms.

In an exemplary embodiment of the present application, R2 is a substituted or unsubstituted amino group, and R1 may be a substituted aryl group having 21 to 60 carbon atoms or a substituted aryl group having 2 to 60 carbon atoms substituted or unsubstituted heteroaryl.

In an exemplary embodiment of the present application, R1 is a substituted or unsubstituted amino group, and R2 may be a substituted or unsubstituted aryl group having 21 to 60 carbon atoms.

In an exemplary embodiment of the present application, R2 is a substituted or unsubstituted amino group, and R1 may be a substituted or unsubstituted aryl group having 21 to 60 carbon atoms.

Specifically, when one of R1 and R2 of the heterocyclic compound represented by Chemical Formula 1 is an aryl group having 21 to 60 carbon atoms, since an aryl group having 20 or less carbon atoms , the compound can have skeletal stability, so thermal stability of the compound can be achieved.

Furthermore, due to the bulky aryl group with 21 to 60 carbon atoms, a device with low-voltage characteristics and high-efficiency characteristics through fast hole mobility can be implemented by creating steric hindrance of the compound.

Furthermore, in an exemplary embodiment of the present application, R1 is a substituted or unsubstituted amino group, and R2 may be a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.

In an exemplary embodiment of the present application, R2 is a substituted or unsubstituted amino group, and R1 may be a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.

In addition, when one of R1 and R2 of the heterocyclic compound represented by Chemical Formula 1 is a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms, the energy level (T1) value of the triplet state may be HOMO exhibits relatively high values and can form holes for easy injection and transport.

In an exemplary embodiment of the present application, X1 and X2 may each independently be hydrogen, deuterium, a halogen group, a substituted or unsubstituted alkyl group with 1 to 60 carbon atoms, a substituted or unsubstituted alkyl group with 3 to 60 carbon atoms, A substituted or unsubstituted cycloalkyl group having 60 carbon atoms, a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, or a substituted or unsubstituted group having 2 to 60 carbon atoms The heterocyclic group.

In an exemplary embodiment of the present application, X1 and X2 may each independently be hydrogen, deuterium, a halogen group, a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms, a substituted or unsubstituted alkyl group having 3 to 40 carbon atoms, A substituted or unsubstituted cycloalkyl group having 40 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, or a substituted or unsubstituted group having 2 to 40 carbon atoms The heterocyclic group.

In an exemplary embodiment of the present application, X1 and X2 may each independently be hydrogen, deuterium, a halogen group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkyl group having 3 to 20 carbon atoms, A substituted or unsubstituted cycloalkyl group having 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted group having 2 to 20 carbon atoms The heterocyclic group.

In another exemplary embodiment, X1 and X2 are each independently hydrogen, deuterium, a halogen group, a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, a group having 3 to 60 carbon atoms Atoms of substituted or unsubstituted cycloalkyl.

In yet another exemplary embodiment, each of X1 and X2 is independently hydrogen, deuterium or a halogen group.

In yet another exemplary embodiment, X1 and X2 are each independently hydrogen or deuterium.

In yet another exemplary embodiment, each of X1 and X2 is independently a substituted or unsubstituted aryl or a substituted or unsubstituted heterocyclic group.

In yet another exemplary embodiment, X1 and X2 are hydrogen or deuterium.

In yet another exemplary embodiment, X1 and X2 are hydrogen.

In yet another exemplary embodiment, X1 and X2 are deuterium.

In an exemplary embodiment of the present application, m of Chemical Formula 1 may be an integer of 0 to 3.

In an exemplary embodiment of the present application, n of Chemical Formula 1 may be an integer of 0 to 5. Referring to FIG.

In an exemplary embodiment of the present application, m is 3. In an exemplary embodiment of the present application, m is 2. In an exemplary embodiment of the present application, m is 1. In an exemplary embodiment of the present application, m is 0.

In an exemplary embodiment of the present application, n is 5. In an exemplary embodiment of the present application, n is 4. In an exemplary embodiment of the present application, n is 3. In an exemplary embodiment of the present application, n is 2. In an exemplary embodiment of the present application, n is 1. In an exemplary embodiment of the present application, n is 0.

In an exemplary embodiment of the present application, when m is 2 or higher, X1 in parentheses are the same as or different from each other.

In an exemplary embodiment of the present application, when n is 2 or higher, X2 in parentheses are the same or different from each other.

[化學式3]

在化學式2和化學式3中， L1、L2、R1、R2、X1、X2、a、b、m以及n的定義與化學式1中的定義相同， L3到L6各自獨立地為直接鍵或具有6個到60個碳原子的經取代或未經取代的伸芳基， c到f各自為0到3的整數，且在c到f各自為2或高於2時，括弧中的取代基彼此相同或不同，且 R3到R6各自獨立地為具有6個到60個碳原子的經取代或未經取代的芳基、具有2個到60個碳原子的經取代或未經取代的雜芳基。 In an exemplary embodiment of the present application, Chemical Formula 1 may be represented by Chemical Formula 2 or Chemical Formula 3 below. [chemical formula 2]

[chemical formula 3]

In Chemical Formula 2 and Chemical Formula 3, the definitions of L1, L2, R1, R2, X1, X2, a, b, m, and n are the same as those in Chemical Formula 1, and L3 to L6 are each independently a direct bond or have 6 A substituted or unsubstituted aryl group of up to 60 carbon atoms, c to f are each an integer of 0 to 3, and when c to f are each 2 or higher than 2, the substituents in the brackets are the same as each other or different, and R3 to R6 are each independently substituted or unsubstituted aryl having 6 to 60 carbon atoms, substituted or unsubstituted heteroaryl having 2 to 60 carbon atoms.

In an exemplary embodiment of the present application, L3 to L6 may each independently be a direct bond or a substituted or unsubstituted arylene group having 6 to 60 carbon atoms.

In an exemplary embodiment of the present application, L3 to L6 may each independently be a direct bond or a substituted or unsubstituted arylene group having 6 to 40 carbon atoms.

In an exemplary embodiment of the present application, L3 to L6 may each independently be a direct bond or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.

In an exemplary embodiment of the present application, L3 to L6 may each independently be a direct bond or a substituted or unsubstituted phenylene group.

In an exemplary embodiment of the present application, L3 is a direct bond. In an exemplary embodiment of the present application, L4 is a direct bond. In an exemplary embodiment of the present application, L5 is a direct bond. In an exemplary embodiment of the present application, L6 is a direct bond.

In an exemplary embodiment of the present application, L3 is a phenylene group. In an exemplary embodiment of the present application, L4 is a phenylene group. In an exemplary embodiment of the present application, L5 is a phenylene group. In an exemplary embodiment of the present application, L6 is a phenylene group.

In an exemplary embodiment of the present application, each of c to f is an integer of 0 to 3, and when each of c to f is 2 or higher, substituents in parentheses may be the same as or different from each other.

In an exemplary embodiment of the present application, c is 0. In an exemplary embodiment of the present application, c is 1. In an exemplary embodiment of the present application, c is 2. In an exemplary embodiment of the present application, c is 3.

In an exemplary embodiment of the present application, d is 0. In an exemplary embodiment of the present application, d is 1. In an exemplary embodiment of the present application, d is 2. In an exemplary embodiment of the present application, d is 3.

In an exemplary embodiment of the present application, e is 0. In an exemplary embodiment of the present application, e is 1. In an exemplary embodiment of the present application, e is 2. In an exemplary embodiment of the present application, e is 3.

In an exemplary embodiment of the present application, f is 0. In an exemplary embodiment of the present application, f is 1. In an exemplary embodiment of the present application, f is 2. In an exemplary embodiment of the present application, f is 3.

In an exemplary embodiment of the present application, when c is 2 or higher, L3 in parentheses are the same or different from each other.

In an exemplary embodiment of the present application, when d is 2 or higher, L4 in parentheses are the same or different from each other.

In an exemplary embodiment of the present application, when e is 2 or higher, L5 in parentheses are the same or different from each other.

In an exemplary embodiment of the present application, when f is 2 or higher, L6 in parentheses are the same or different from each other.

In an exemplary embodiment of the present application, R3 to R6 may each independently be a substituted or unsubstituted aryl group having 6 to 60 carbon atoms; a substituted or unsubstituted aryl group having 2 to 60 carbon atoms Unsubstituted heteroaryl.

In an exemplary embodiment of the present application, R3 to R6 may each independently be a substituted or unsubstituted aryl group having 6 to 40 carbon atoms; a substituted or unsubstituted aryl group having 2 to 40 carbon atoms Unsubstituted heteroaryl.

In an exemplary embodiment of the present application, R3 to R6 may each independently be a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; a substituted or unsubstituted aryl group having 2 to 20 carbon atoms Unsubstituted heteroaryl.

In an exemplary embodiment of the present application, R3 and R4 are each independently a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, a substituted or unsubstituted aryl group having 2 to 60 carbon atoms Substituted heteroaryl, and R5 and R6 can be substituted or unsubstituted aryl having 6 to 60 carbon atoms.

In an exemplary embodiment of the present application, R3 and R4 are each independently a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, a substituted or unsubstituted aryl group having 2 to 40 carbon atoms Substituted heteroaryl, and R5 and R6 can be substituted or unsubstituted aryl having 6 to 40 carbon atoms.

In an exemplary embodiment of the present application, R3 and R4 are each independently a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted aryl group having 2 to 20 carbon atoms Substituted heteroaryl, and R5 and R6 can be substituted or unsubstituted aryl having 6 to 20 carbon atoms.

In an exemplary embodiment of the present application, R3 to R6 may be substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, and substituted or Unsubstituted dimethylfluorenyl.

In an exemplary embodiment of the present application, R3 to R6 may be unsubstituted or substituted with one or more deuterium phenyl, biphenyl, or naphthyl; or substituted or unsubstituted dimethylfluorene base.

In an exemplary embodiment of the present application, the deuterium content of the heterocyclic compound represented by Chemical Formula 1 may be 0% to 100%.

In an exemplary embodiment of the present application, the deuterium content of the heterocyclic compound represented by Chemical Formula 1 may be 10% to 100%.

In an exemplary embodiment of the present application, the deuterium content of the heterocyclic compound represented by Chemical Formula 1 may be 20% to 100%.

In an exemplary embodiment of the present application, the deuterium content of the heterocyclic compound represented by Chemical Formula 1 may be 30% to 100%.

In an exemplary embodiment of the present application, the deuterium content of the heterocyclic compound represented by Chemical Formula 1 may be 40% to 100%.

According to an exemplary embodiment of the present application, Chemical Formula 1 may be represented by any one of the following compounds, but is not limited thereto.

In addition, various substituents may be introduced into the structure of Chemical Formula 1 to synthesize compounds having inherent properties of the introduced substituents. For example, it is possible to introduce into the Materials that meet the conditions required for each organic material layer are synthesized in the core structure.

In addition, it is possible to finely adjust the energy bandgap by introducing various substituents into the structure of Chemical Formula 1, and at the same time, it is possible to improve characteristics at the interface between organic materials and diversify uses of the materials.

Meanwhile, the heterocyclic compound has a high glass transition temperature (Tg), and thus has excellent thermal stability. The increase in thermal stability becomes an important factor in providing drive stability to the device.

A heterocyclic compound according to an exemplary embodiment of the present application may be prepared through a multi-step chemical reaction. Some intermediate compounds are prepared first, and the compound of Chemical Formula 1 can be prepared according to the intermediate compounds. More specifically, the heterocyclic compound according to the exemplary embodiment of the present application can be prepared based on the preparation examples to be described below.

Another exemplary embodiment of the present application provides an organic light emitting device including the heterocyclic compound represented by Chemical Formula 1. Referring to FIG. "Organic light emitting device" may be referred to, for example, "organic light emitting diode", "organic light emitting diodes (OLED)", "OLED device", and "organic electroluminescence device", etc. term to express.

The heterocyclic compound can be formed as an organic material layer not only by a vacuum deposition method but also by a solution coating method at the time of manufacturing an organic light-emitting device. Here, the solution coating method means spin coating, dip coating, inkjet printing, screen printing, spray coating method, roll coating, and the like, but is not limited thereto.

Specifically, an organic light emitting device according to an exemplary embodiment of the present application includes a first electrode, a second electrode, and an organic material layer having one or more layers disposed between the first electrode and the second electrode, wherein One or more layers of the organic material layers include the heterocyclic compound represented by Chemical Formula 1. When the organic material layer includes the heterocyclic compound represented by Chemical Formula 1, the luminous efficiency and service life of the organic light emitting device are excellent.

In an exemplary embodiment of the present application, the first electrode may be a positive electrode, and the second electrode may be a negative electrode.

In another exemplary embodiment, the first electrode may be a negative electrode, and the second electrode may be a positive electrode.

The organic material layer may include a hole transport assisting layer having one or more layers. In this specification, the "hole transport auxiliary layer" is a layer disposed between the hole transport layer and the light emitting layer of an organic light-emitting device, and means to improve the organic layer by preventing electrons from passing through the opposite side of the electron transport layer. A functional layer for the purpose of brightness and efficiency and lifetime characteristics of a light emitting device, and may be referred to as an "electronic protection layer" or a "prime layer". The material constituting the hole transport auxiliary layer can be determined by the light emitting material used for the light emitting layer.

The organic material layer of the organic light emitting device according to an exemplary embodiment of the present application includes a hole transport auxiliary layer having one or more layers, and the hole transport auxiliary layer includes a heterocyclic compound represented by Chemical Formula 1. Referring to FIG. When the hole transport auxiliary layer among the organic material layers includes the heterocyclic compound represented by Chemical Formula 1, the luminous efficiency and service life of the organic light emitting device are better.

The organic material layer of the organic light emitting device according to an exemplary embodiment of the present application includes a hole transport layer having one or more layers, and the hole transport layer includes a heterocyclic compound represented by Chemical Formula 1. When the hole transport layer among the organic material layers includes the heterocyclic compound represented by Chemical Formula 1, the luminous efficiency and service life of the organic light emitting device are better.

The organic light-emitting device of the present invention may further comprise one or two or more than two layers selected from the group consisting of: light-emitting layer, hole injection layer, hole transport layer, electron injection layer, electron transport layer, hole auxiliary layer and hole blocking layer.

An organic light emitting device according to an exemplary embodiment of the present application may be manufactured by typical manufacturing methods and materials of an organic light emitting device except that the above-mentioned heterocyclic compound is used to form an organic material layer.

1 to 3 illustrate a stacking sequence of electrodes and organic material layers of an organic light emitting device according to an exemplary embodiment of the present application. However, the scope of the present application is not intended to be limited by these drawings, and structures of organic light emitting devices known in the art may also be applied to the present application.

According to FIG. 1 , an organic light emitting device in which a positive electrode 200 , an organic material layer 300 and a negative electrode 400 are sequentially stacked on a substrate 100 is shown. However, the organic light emitting device is not limited to such a structure, and as in FIG. 2 , an organic light emitting device in which a negative electrode, an organic material layer, and a positive electrode are sequentially stacked on a substrate may also be implemented.

FIG. 3 exemplifies the case where the organic material layer is multilayered. The organic light emitting device according to FIG. 3 includes a hole injection layer 301 , a hole transport layer 302 , a light emitting layer 303 , a hole blocking layer 304 , an electron transport layer 305 and an electron injection layer 306 . However, the scope of the present application is not limited by the stacked structure as described above, and layers other than the light emitting layer may be omitted and another necessary functional layer may be further added as necessary.

The heterocyclic compound represented by Chemical Formula 1 may constitute one or more layers of a hole transport layer or an electron blocking layer of an organic light emitting device alone. However, the heterocyclic compound represented by Chemical Formula 1 may be mixed with another material to constitute a hole transport layer or an electron blocking layer, as needed.

In the organic light emitting device according to the exemplary embodiment of the present application, materials other than the heterocyclic compound of Chemical Formula 1 will be exemplified below, but these materials are only illustrative and not intended to limit the scope of the present application, And can be replaced by materials well known in the art.

As the positive electrode material, a material having a relatively high work function can be used, and a transparent conductive oxide, a metal, or a conductive polymer, and the like can be used. Specific examples of positive electrode materials include: metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (indium zinc oxide; IZO); combinations of metals and oxides, such as ZnO:Al or SnO ₂ :Sb; conductive polymers, such as poly(3-methylthiophene), poly[3,4-(ethylene-1, 2-dioxy)thiophene] (PEDT), polypyrrole, and polyaniline; and the like, but not limited thereto.

As the negative electrode material, a material having a relatively low work function can be used, and a metal, a metal oxide, or a conductive polymer, and the like can be used. Specific examples of negative electrode materials include: metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; multilayer structure materials such as LiF/Al or LiO ₂ /Al; and the like, but not limited thereto.

As the hole injection material, well-known hole injection materials can also be used, and it is possible to use, for example, phthalocyanine compounds (such as copper phthalocyanine) disclosed in US Pat. , p. 677 (1994)], the starburst-type amine derivatives described in, for example, tris(4-carbazinyl-9-ylphenyl)amine (TCTA), 4,4 ',4"-tris[phenyl(m-tolyl)amino]triphenylamine (m-MTDATA), 1,3,5-tris[4-(3-methylphenylphenylamino)phenyl]benzene (m- MTDAPB), polyaniline/dodecylbenzenesulfonic acid or poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) (which is a soluble conductive polymer), polyaniline/ Camphorsulfonic acid or polyaniline/poly(4-styrene-sulfonate), and the like.

As the hole transport material, pyrazoline derivatives, arylamino derivatives, stilbene derivatives, triphenyldiamine derivatives, and the like can be used, and low molecular weight or polymer materials can also be used.

As electron transport materials, it is possible to use oxadiazole derivatives, anthraquinone dimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinone di Methane and its derivatives, fluorenone derivatives, diphenylethylene dicyanide and its derivatives, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and its derivatives, and the like, and may also be used Low molecular weight materials and polymeric materials.

As an electron injection material, for example, LiF is typically used in the art, but the present application is not limited thereto.

As the light emitting material, a red light emitting material, a green light emitting material or a blue light emitting material may be used, and if necessary, two or more light emitting materials may be mixed and used. In addition, fluorescent materials can also be used as light-emitting materials, but can also be used as phosphorescent materials. As a light-emitting material, it is also possible to use alone a material that emits light by combining holes and electrons injected from the positive and negative electrodes, respectively, but a material that participates in light emission together with a host material and a dopant material may also be used.

An organic light emitting device according to an exemplary embodiment of the present application may be a top emission type, a bottom emission type, or a dual emission type according to materials to be used.

Heterocyclic compounds according to exemplary embodiments of the present application can function even in organic electronic devices including organic solar cells, organic photoconductors, organic transistors, and the like based on principles similar to those applied to organic light-emitting devices .

Hereinafter, the present specification will be described in more detail through examples, but these examples are only provided to illustrate the present application and are not intended to limit the scope of the present application.

（ 1 ） 製備化合物 2-4 < Preparation Example 1> Preparation of Compound 2

( 1 ) Preparation of compounds 2-4

Compound 2-5 (2-iodonaphthalene-1-ol) (47.0 g, 174.75 mmol), (2-chloro-6-fluorophenyl) boronic acid (34.2 g, 192.22 mmol), Pd (pph ₃ ) ₄ (201.93 g, 174.75 mmol) and K ₂ CO ₃ (24.15 g, 174.75 mmol) were added to a mixture of 1,4-dioxane (750 mL) and water (150 mL), and The resulting mixture was stirred at 120 °C for 4 hours (h). The temperature was lowered to room temperature, the aqueous layer was separated, and the organic layer was separated by washing the organic layer with water again. A slurry was generated by introducing anhydrous magnesium sulfate into the collected organic layer, followed by filtration and concentration under reduced pressure. Compound 2-4 (2-(2-chloro-6-fluorophenyl)naphthalene-1-ol) (43.4 g , 159.3 mmol, 91% yield). ( 2 ) Preparation of compound 2-3

Compound 2-4 (2-(2-chloro-6-fluorophenyl)naphthalene-1-ol) (43.4 g, 159.3 mmol) and _KCO ( _66.04 g, 477.89 mmol) were added to N-methyl-2-pyrrolidone (hereinafter, NMP) (460 ml), and the resulting mixture was stirred at 140°C for 3 hours. Thereafter, after about 1 hour, the reaction product was cooled to room temperature and slowly introduced into 500 ml of water. The precipitated solid was filtered, and after the filtered solid was dissolved in tetrahydrofuran (hereinafter, THF), the resulting solution was treated with anhydrous magnesium sulfate, filtered, and then concentrated under reduced pressure. The concentrated compound was slurried with a small amount of tetrahydrofuran and excess hexane and filtered. In order to purify the filtered compound, the filtered compound was separated by silica gel chromatography using hexane and ethyl acetate to prepare compound 2-3 (7-chloronaphtho[1,2-b]benzofuran) (37.6 g, 148.83 mg Mole, 93.431% yield). ( 3 ) Preparation of compound 2-2

After dissolving compound 2-3 (7-chloronaphtho[1,2-b]benzofuran) (37.6 g, 148.83 mmol) in dichloromethane (hereinafter, DCM) (400 mL), The resulting solution was stirred in an ice-water bath using a needle, then bromine (26.43 g, 163.71 mmol) was added dropwise thereto, and then the resulting mixture was stirred at room temperature for 3 hours to obtain compound 2-2 (5 -bromo-7-chloronaphtho[1,2-b]benzofuran) (48.6 g, 146.7 mmol, 98.564% yield). ( 4 ) Preparation of compound 2-1

Compound 2-2 (5-bromo-7-chloronaphtho[1,2-b]benzofuran) (48.6 g, 146.57 mmol), dibenzo[b,d]furan-4-ylboronic acid (A) (32.63 g, 153.89 mmol), Pd(pph ₃ ) ₄ (8.47 g, 7.33 mmol) and K ₂ CO ₃ (60.77 g, 439.7 mmol) were added to 1,4-diox Alkanes (800 ml) and distilled water (200 ml), and the resulting mixture was reacted under reflux for 5 hours. After the reaction was completed, 100 ml of dichloromethane (hereinafter, MC) and 150 ml of water were added to the reaction solution for disposal, and then the resulting product was placed in a separatory funnel to separate an organic layer. After the organic layer was dried over anhydrous _MgSO4 and the solvent was removed by rotary evaporator, the organic layer was slurried by acetone and hexane to obtain compound 2-1 (7-chloro-5-dibenzofuran-4-yl- Naphtho[1,2-b]benzofuran) (55 g, 131.31 mmol, 89.588% yield). ( 5 ) Preparation of Compound 2(C)

Compound 2-1 (7-chloro-5-dibenzofuran-4-yl-naphtho[1,2-b]benzofuran) (55.0 g, 131.31 mmol), bis(4-biphenyl base) amine (B) (43.06 g, 131.31 mmol), Pd ₂ (dba) ₃ (6.01 g, 6.57 mmol), Xphos (6.26 g, 13.13 mmol) and NaOt-Bu (37.86 g, 393.92 mmol) was added to xylene (1000 ml), and the resulting mixture was stirred at 125°C under reflux for 5 hours. After the reaction was completed, MC was added to the reaction solution and dissolved, followed by extraction with distilled water, the organic layer was dried over anhydrous magnesium sulfate, the solvent was removed by a rotary evaporator, and then the residue was passed through column chromatography (MC:hexane=1 :3) Purification to obtain compound 2 (5-dibenzofuran-4-yl-N,N-bis(4-phenylphenyl)naphtho[1,2-b]benzofuran-7-amine) (C) (67 g, 95.195 mmol, 72.499% yield).

＜ 製備實例 2＞ 製備化合物 418(F)

（ 1 ） 製備化合物 418-2 The target compound C in the following table 1 was synthesized in the same manner as in the preparation example 1, except that the dibenzo[b, d in the preparation example 1 was replaced by intermediate A and intermediate B in the following table 1, respectively ]furan-4-ylboronic acid and bis(4-biphenylyl)amine. [Table 1]

< Preparation Example 2> Preparation of Compound 418(F)

( 1 ) Preparation of compound 418-2

Compound 418-3 (7-chloronaphtho[1,2-b]benzofuran) (50.0 g, 197.86 mmol), 4-dibenzofuran-4-yl-phenyl-boronic acid (D) (64.89 g, 220.73 mmol), Pd ₂ (dba) ₃ (9.06 g, 9.89 mmol), Xphos (9.43 g, 19.79 mmol), and K ₂ CO ₃ (82.03 g, 593.59 mmol) It was added to a mixture of 1,4-dioxane (1000 mL) and distilled water (250 mL), and the resulting mixture was stirred at 120° C. for 4 hours. The temperature was lowered to room temperature, the aqueous layer was separated, and the organic layer was separated by washing the organic layer with water again. A slurry was generated by introducing anhydrous magnesium sulfate into the collected organic layer, followed by filtration and concentration under reduced pressure. Compound 418-2(7-(4-dibenzofuran-4-ylphenyl)naphtho[1,2 -b] benzofuran) (80 g, 173.72 mmol, 87.796% yield). ( 2 ) Preparation of compound 418-1

After dissolving compound 418-2 (7-(4-dibenzofuran-4-ylphenyl)naphtho[1,2-b]benzofuran) (80.0 g, 173.72 mmol) in DCM (800 mL), the resulting solution was stirred in an ice-water bath, then bromine (26.43 g, 163.71 mmol) was added dropwise thereto using a needle, and then the resulting mixture was stirred at room temperature for 3 hours to obtain compound 418 -1(5-Bromo-7-(4-dibenzofuran-4-ylphenyl)naphtho[1,2-b]benzofuran) (80 g, 148.31 mmol, 85.373% yield) . ( 3 ) Preparation of compound 418

Compound 418-1 (5-bromo-7-(4-dibenzofuran-4-ylphenyl)naphtho[1,2-b]benzofuran) (80 g, 148.31 mmol), 9 , 9-Dimethyl-N-phenyl-9H-fluoren-2-amine (E) (46.56 g, 163.14 mmol), Pd ₂ (dba) ₃ (6.79 g, 7.42 mmol), Xphos ( 7.07 g, 14.83 mmol) and NaOt-Bu (42.76 g, 444.92 mmol) were added to xylene (1200 mL), and the resulting mixture was stirred at 125°C under reflux for 5 hours. After the reaction was completed, MC was added to the reaction solution and dissolved, followed by extraction with distilled water, the organic layer was dried over anhydrous magnesium sulfate, the solvent was removed by a rotary evaporator, and then the residue was passed through column chromatography (MC:hexane=1 :3) Purification to obtain compound 418 (7-(4-dibenzofuran-4-ylphenyl)-N-(9,9-dimethylfluoren-2-yl)-N-phenyl-naphtho [1,2-b]benzofuran-5-amine) (F) (55 g, 73.936 mmol, 49.853% yield).

＜ 製備實例 3＞ 製備化合物 384

The target compound F was synthesized in the same manner as in Preparation Example 2, except that Intermediate D and Intermediate were used to replace 4-dibenzofuran-4-yl-phenyl-boronic acid and 9 in Preparation Example 2, respectively, 9-Dimethyl-N-phenyl-9H-fluoren-2-amine. [Table 2]

< Preparation Example 3> Preparation of Compound 384

After dissolving compound 2 (10.0 g, 14.21 mmol) and trifluoromethanesulfonic acid (8.78 mL, 99.46 mmol) in _D6 -benzene (100 mL), the resulting solution was stirred at 60 °C for 4 Hour. After the reaction was completed, the resulting product was neutralized with aqueous K ₃ PO ₄ at room temperature, and then extracted with dichloromethane (DCM) and distilled water (H ₂ O).

The re-extracted reaction product was purified by column chromatography (DCM:Hex = 1:1) and recrystallized with methanol to obtain the target compound 384 (9 g, 12.211 mmol, 85.945% yield).

Here, Hex means hexane, and DCM:Hex means volume ratio. < Preparation Example 4> Preparation of Compound 524

After dissolving compound 401 (10.0 g, 14.21 mmol) and trifluoromethanesulfonic acid (8.78 mL, 99.46 mmol) in _D6 -benzene (100 mL), the resulting solution was stirred at 60 °C for 4 Hour. After the reaction was completed, the resulting product was neutralized with aqueous K ₃ PO ₄ at room temperature, and then extracted with dichloromethane (DCM) and water (H ₂ O).

The re-extracted reaction product was purified by column chromatography (dichloromethane:hexane=1:1 volume ratio) and recrystallized with methanol, and the resulting product was extracted with dichloromethane/H ₂ O. The reaction product was purified by column chromatography (DCM:Hex = 1:1) and recrystallized with methanol to obtain the target compound 524 (8 g, 10.854 mmol, 76.395% yield).

（ 1 ） 製備化合物 534-1 Here, Hex means hexane, and DCM:Hex means volume ratio. < Preparation Example 5> Preparation of Compound 534(F)

( 1 ) Preparation of compound 534-1

Compound 534-1 was prepared in the same manner as the method for preparing Compound 2-1 in Preparation Example 1. That is, Compound 534-2 is the same as Compound 2-2 in Preparation Example 1, and Compound 534-1 is the same as Compound 2-1 in Preparation Example 1. ( 2 ) Preparation of compound 534

Compound 534-1, 4-(biphenyl-4-ylamino)phenylboronic acid (H) (11.71 g, 26.26 mmol), 7-chloro-5-dibenzofuran-4-yl-naphtho [1,2-b]benzofuran (10.0 g, 23.87 mmol), Pd(dba) ₂ (0.41 g, 1.19 mmol), Xphos (1.29 mL, 2.39 mmol) and potassium carbonate (9.9 g, 71.62 mmol) was added to 1,4-dioxane (200 mL) and water (50 mL), and the resulting mixture was stirred at 120 °C for 4 hours, and then extracted with water and MC to concentrate the organic layer . Silica gel was added to the concentrated crude mixture, concentrated and adsorbed, and then separated by column chromatography (MC:Hex = 1:4). After concentration of the separated solution, and then slurrying with methanol (MeOH), the solid was filtered to obtain compound 534 (N-[4-(5-dibenzofuran-4-ylnaphtho[1,2-b ]benzofuran-7-yl)phenyl]-4-phenyl-N-(4-phenylphenyl)aniline). (15 g, 19.233 mmol, 80.56% yield)

The target compound I in Table 3 below was synthesized in the same manner as in Preparation Example 5, except that in Preparation Example 5, Intermediate G in Table 3 below was used instead of dibenzo[b,d]furan-4 -ylboronic acid (D), and use intermediate H in Table 3 below in place of 4-(biphenyl-4-ylamino)phenylboronic acid (H). [table 3]

Compounds were prepared in the same manner as in Preparation Examples, and their synthesis confirmation results are shown in Table 4 and Table 5 below. Specifically, Table 4 shows the measured values of ¹ H NMR (CDCl ₃ , 200 Mz), and Table 5 shows the measured values of Field Desorption Mass Spectrometry (FD-MS).

[Table 4] compound ¹ H NMR (CDCl ₃ , 200Mz) 2 δ= 8.97(1H, d), 8.18(1H, d), 7.98~8.08(3H, m), 7.75(4H, d), 7.25~7.55(23H, m) 3 δ= 8.97(1H, d), 8.18(1H, d), 7.98~8.08(3H, m), 7.86~7.90 (2H, d), 7.51~7.64(5H, m), 7.24~7.39(11H, m ) 7.00~7.08(3H, m), 6.91(2H, d),1.69 (6H, s) 5 δ= 8.97(1H, d), 8.18(1H, d), 7.98~8.08(3H, m), 7.76~7.70 (2H, t), 7.54~7.64(3H, m), 7.05~7.39(9H, m ), 6.91~7.09(7.H, m) 11 δ= 8.97(1H, d), 8.18(1H, d), 7.98(1H, d) 7.86~7.96(7H, m), 7.28~7.63(19H, m), 7.16(1H, d), 6.91(1H , d) 15 δ= 8.97(1H, d), 8.18(1H, d), 7.98(1H, d), 7.00~7.90 (3H, m), 7.53~7.69 (6H, m), 7.00~7.08(3H, m), 6.91(2H, d),1.69(6H, s) 20 δ= 8.97(1H, d), 8.18(1H, d), 7.98~8.08(3H, m), 7.25~7.64 (12H, m), 7.11(2H, s), 6.91(2H, d) twenty three δ= 8.97(1H, d), 8.18(1H, d), 7.98~8.03(2H, m), 7.76~7.90 (4H, m), 7.16~7.38 (15H, m), 7.08(3H, m), 6.91(1H, d) 30 δ= 8.97(1H, d), 8.18(1H, d), 7.98(1H, d), 7.18~7.82 (31H, m), 6.91(1H, d) 42 δ= 8.97(1H, d), 8.18(1H, d), 8.02~8.08(4H, m), 7.75(4H, d), 7.34~7.64 (25H, m), 7.25(1H, m), 6.91( 1H, d) 45 δ= 8.97(1H, d), 8.18(1H, d), 8.02~8.08(3H, m), 7.75~7.82 (4H, m), 7.24~7.64 (13H, m), 6.91~7.08 (7H, m ) 50 δ= 8.97(1H, d), 8.18(1H, d), 8.02~8.08(2H, m), 7.75~7.88 (7H, m), 7.24~7.64 (18H, m), 7.00~7.08 (3H, m ), 6.91(1H, d) 51 δ= 8.97(1H, d), 8.18(1H, d), 8.02~8.08(2H, m), 7.75~7.83 (3H, m), 7.24~7.64 (16H, m), 7.00~7.08 (3H, m ), 6.91(1H, d) 57 δ= 8.97(1H, d), 8.18(1H, d), 7.98~8.08(2H, m), 7.79(2H, d), 7.24~7.64 (15H, m), 6.91~7.08 (7H, m) 60 δ= 8.97(1H, d), 8.18(1H, d), 7.98~8.08(3H, m), 7.25~7.78(25H, m), 7.11(2H, s), 6.91(1H, d) 61 δ= 8.97(1H, d), 8.50(1H, d), 8.18~8.20(2H, t), 8.07~8.95(4H, m), 7.77(1H, t), 7.52~7.64 (4H, m), 7.24~7.39 (10H, m), 6.91~7.08 (7H, m) 62 δ= 8.97(1H, d), 8.50(1H, d), 8.18~8.20(2H, t), 7.98~8.08(4H, m), 7.77(1H, t), 7.24~7.64 (19H, m), 7.00~7.08 (3H, m), 6.91(1H, d) 70 δ= 8.97(1H, d), 8.50(1H, d), 8.18~8.20(2H, t), 8.02~8.09(3H, m), 7.34~7.77 (18H, m), 7.25 (1H, m), 6.91(1H, d) 82 δ= 8.97~9.00(2H, m), 8.18(1H, d), 7.98(1H, d), 7.24~7.75 (26H, m), 7.08 (3H, m), 6.91(1H, d) 84 δ= 8.97~9.00(3H, m), 8.18(1H, d), 7.98(1H, d), 7.24~7.75 (26H, m), 7.11 (2H, s), 6.91(1H, d) 92 δ= 8.97(1H, d), 8.18(1H, d), 8.02~8.03(3H, m), 7.25~7.82 (29H, m), 7.11 (2H, s), 6.91(1H, d) 93 δ= 8.97(1H, d), 8.18(1H, d), 8.02~8.08(2H, m), 7.75~7.88 (5H, m), 7.25~7.64 (17H, m), 7.00~7.08 (6H, m ), 95 δ= 8.97(1H, d), 8.18(1H, d), 8.02~8.08(2H, m), 7.75~7.88 (5H, m), 7.25~7.64 (22H, m), 7.00~7.08 (3H, m ), 6.91(1H, d) 114 δ= 8.97(1H, d), 8.45(1H, d), 8.18(1H, d), 8.03(1H, d), 7.25~7.75(27H, m), 6.91 (1H, d) 115 δ= 8.97(1H, d), 8.45(1H, d), 8.18(1H, d), 8.03(1H, d), 7.17~7.93(4H, m), 7.26~7.64(21H, m), 120 δ= 8.97(1H, d), 8.55(1H, d), 8.45(1H, d), 8.32(1H, d), 8.18(1H, d), 7.93(1H, d), 7.25~7.78(24H, m), 7.11 (2H, s), 6.91 (1H, d) 134 δ= 8.97(1H, d), 8.45(1H, d), 8.18~8.24(4H, m), 7.93~7.94(2H, d), 7.24~7.64 (21H, m), 6.91~7.08(4H, m ) 147 δ= 8.97(1H, d), 8.55(1H, d), 8.32(1H, d), ), 8.18(1H, d), ), 8.03(1H, d), 7.79~7.94(5H, m), 7.55~7.70(5H, m), 7.25~7.46(12H, m), 7.00~7.08(3H, m) 6.91 (1H, d), 1.69(6H, s) 155 δ= 8.97(1H, d), 8.55(1H, d), 8.32(1H, d), 8.18(1H, d), 8.03(1H, d), 7.79~7.94(5H, m), 7.08~7.46( 12H, m),7.00~7.08(3H, m) 235 δ= 8.97(1H, d), 8.18(1H, d), 8.09(1H, d), 7.86~7.96(5H, m) 7.55~7.76(6H, m), 7.08~7.38(24H, m), 6.91 (1H, d), 1.69(6H, s) 245 δ= 8.97(1H, d), 8.18(1H, d), 8.09(2H, d), 7.89(2H, s), 7.75~7.78(4H, m), 7.59~7.64(2H, m), 7.08~ 7.49(26H, m), 6.91(1H, d) 250 δ= 8.97(1H, d), 8.18(1H, d), 8.09(1H, d), 7.89(1H, s), 7.18~7.75(36H, m), 6.91(1H, d) 351 δ= 8.97(1H, d), 8.18(1H, d), 8.04(3H, s), 7.86~7.90(2H, m),7.75(4H, t), 7.16~7.64(22H, m),7.00~ 7.08(3H, m), 6.91(1H, d) 382 δ= 8.97(1H, d), 8.18(1H, d), 7.75(4H, t), 7.34~7.64(28H, m), 7.25(1H, d), 6.91(1H, d) 383 δ= 8.97(1H, d), 8.18(1H, d), 7.98~8.08(3H, m), 7.51~7.64(4H, m), 7.25~7.39(5H, m), 6.91(1H, d) 386 δ= 8.12~8.22(3H, m), 7.37~7.82(23H, m) 387 δ= = 7.98~8.22(6H, m),7.82(1H, d) 7.50~7.69(6H, m),7.31~7.39(2H, d) 402 δ= 7.98~8.22(6H, m), 7.82~7.90(3H, m), 7.50~7.69(5H, m), 7.24~7.39(8H, m), 7.00~7.08(3H, m) 403 δ= 7.98~8.22(6H, m), 7.81~7.82(2H, m), 7.24~7.69(14H, m), 7.00~7.08(3H, m) 406 δ= 8.12~8.22(3H, m), 7.98~8.03(2H, m), 7.76~7.90(5H, m), 7.50~7.69(6H, m), 7.16~7.39(8H, m), 7.00~7.08 (3H, m) 407 δ= 8.12~8.22(3H, m), 7.24~7.69(17H, m), 7.00~7.08(3H, m) 410 δ= 8.97(1H, d), 8.18(1H, d), 7.98~8.08(3H, m), 7.51~7.64(4H, m), 7.25~7.39(5H, m), 6.91(1H, d) 418 δ= 7.98~8.22(6H, m), 7.82~7.90(3H, m), 7.55~7.69(3H, m), 7.16~7.39(12H, m), 7.00~7.08(3H, m) 420 δ= 8.08~8.22(5H, m), 7.25~7.82(25H, m), 7.11 (2H, s) 423 δ= 8.55(1H, d), 8.45(1H, d), 8.32(1H, d), 7.82~7.93(4H, m), 7.49~7.70(8H, m), 7.24~7.38(10H, m), 7.00~7.08(3H, m) 428 δ= 8.55(1H, d), 8.45(1H, d), 8.32(1H, d), 7.82~7.93(4H, m), 7.49~7.70(8H, m), 7.24~7.38(10H, m), 7.11 (2H, s) 7.00~7.08(3H, m) 430 δ= 8.55(1H, d), 8.45(1H, d), 8.32(1H, d), 7.82~7.93(4H, m), 7.49~7.70(8H, m), 7.11 (2H, s), 6.91( 1H, d) 435 δ= 8.55(1H, d), 8.45(1H, d), 8.32(1H, d), 8.12~8.22(5H, m), 7.93(1H, d), 7.81~7.82(2H, t), 7.49~ 7.70(8H, m), 7.24~7.38(10H, m), 6.91(1H, d) 438 δ= 8.55(1H, d), 8.45(1H, d), 8.32(1H, d), 7.82~7.93(4H, m), 7.49~7.70(8H, m), 7.24~7.38(10H, m), 7.00~7.08(3H, m) 450 δ= 8.97(1H, d), 8.18(1H, d), 8.02~8.03(3H, m), 7.25~7.82 (29H, m), 7.11 (2H, s), 6.91(1H, d) 455 δ= 8.97(1H, d), 8.18(1H, d), 8.02~8.03(3H, m), 7.25~7.82 (29H, m), 7.11 (2H, s), ), 7.00~7.08(3H, m ), 6.91(1H, d) 480 δ= 8.55(1H, d), 8.45(1H, d), 8.32(1H, d), 8.12~8.22(5H, m), 7.49~7.70(11H, m), 7.00~7.08(3H, m) 489 δ= 8.55(1H, d), 8.45(1H, d), 8.32(1H, d), 8.12~8.22(5H, m), 7.93(1H, d), 7.81~7.82(2H, t), 7.49~ 7.70(11H, m), 7.24~7.25(6H, m), 7.00~7.08(3H, m) 534 δ= 8.97(1H, d), 8.18(1H, d), 7.98~8.03(2H, m), 7.31~7.69(30H, m) 535 δ= 8.97(1H, d), 8.18(1H, d), 7.98(1H, d), 7.28~7.83(31H, m, 7.16(1H, d), 1.69(6H, s) [table 5] compound FD-MS compound FD-MS 2 Molecular weight: 703.84 147 Molecular weight: 759.97 3 Molecular weight: 667.81 155 Molecular weight: 759.97 5 Molecular weight: 551.64 235 Molecular weight: 894.13 11 Molecular weight: 743.91 245 Molecular weight: 777.97 15 Molecular weight: 667.81 250 Molecular weight: 854.06 20 Molecular weight: 727.86 351 Molecular weight: 806.02 twenty three Molecular weight: 743.91 382 Molecular weight: 710.88 30 Molecular weight: 779.94 383 Molecular weight: 710.88 42 Molecular weight: 779.94 386 Molecular weight: 710.88 45 Molecular weight: 627.74 387 Molecular weight: 721.95 50 Molecular weight: 703.84 402 Molecular weight: 667.81 51 Molecular weight: 743.91 403 Molecular weight: 601.70 57 Molecular weight: 627.74 406 Molecular weight: 667.81 60 Molecular weight: 727.86 407 Molecular weight: 743.91 61 Molecular weight: 677.80 410 Molecular weight: 667.81 62 Molecular weight: 753.90 418 Molecular weight: 743.91 70 Molecular weight: 830.00 420 Molecular weight: 727.86 82 Molecular weight: 753.90 423 Molecular weight: 617.77 84 Molecular weight: 777.92 428 Molecular weight: 667.83 92 Molecular weight: 803.96 430 Molecular weight: 683.87 93 Molecular weight: 703.84 435 Molecular weight: 617.77 95 Molecular weight: 820.00 438 Molecular weight: 759.97 114 Molecular weight: 719.90 450 Molecular weight: 683.87 115 Molecular weight: 759.97 455 Molecular weight: 617.77 120 Molecular weight: 743.92 480 Molecular weight: 878.09 134 Molecular weight: 719.90 489 Molecular weight: 693.86 < Experimental example 1> ( 1 ) Manufacturing organic light-emitting device comparative example 1

Trichlorethylene, acetone, ethanol, and distilled water were each sequentially used to ultrasonically wash transparent electrodes obtained from glass for OLEDs (manufactured by Samsung-Corning Co., Ltd.) Indium tin oxide (ITO) The films were left for 5 minutes, and then the ITO films were placed in isopropanol, stored, and then used. Next, the ITO substrate was placed in the substrate holder of the vacuum deposition equipment, and the following 4,4',4"-tris(N,N-(2-naphthyl)-anilino)triphenylamine (2 -TNATA) placed in a cell in a vacuum deposition apparatus.

Subsequently, the air in the chamber was evacuated until the vacuum degree in the chamber reached 10 ^-6 Torr, and then a hole injection layer with a thickness of 600 angstroms was deposited on the ITO by applying current to the cell to evaporate 2-TNATA on the substrate. By placing the following N,N'-bis(α-naphthyl)-N,N'-diphenyl-4,4'-diamine (NPB) in another cell in the vacuum deposition apparatus and applying current To the cell to evaporate the NPB, deposit a hole transport layer with a thickness of 300 Å on top of the hole injection layer.

A hole injection layer and a hole transport layer were formed as described above, and then a blue light-emitting material having the following structure was deposited thereon as a light-emitting layer. Specifically, the blue-light-emitting host material H1 was vacuum-deposited to a thickness of 200 angstroms on one unit in the vacuum deposition apparatus, and the blue-light-emitting dopant material D1 was vacuum-deposited thereon in an amount of 5% based on the host material .

Subsequently, a compound having the following structural formula E1 was deposited as an electron transport layer to a thickness of 300 angstroms.

OLED devices were fabricated by depositing lithium fluoride (LiF) as an electron injection layer to a thickness of 10 angstroms and allowing the Al negative electrode to have a thickness of 1,000 angstroms. Meanwhile, all organic compounds required to fabricate OLED devices were subjected to vacuum sublimation purification at 10 ⁻⁶ Torr to 10 ⁻⁸ Torr for each material, and used to fabricate OLEDs. Comparative Example 2 to Comparative Example 7 and Example 1 to Example 21

An organic electroluminescent device was fabricated in the same manner as in Comparative Example 1 except that the compounds in Table 6 below were used instead of NPB used when forming the hole transport layer in Comparative Example 1.

（ 2 ） 評估有機發光裝置 Compound HT1 to Compound HT6 in Table 3 below are as follows.

( 2 ) Evaluation of organic light-emitting devices

For the organic light-emitting device fabricated as described above, electroluminescence (EL) characteristics were measured using M7000 manufactured by McScience Inc., and at a reference luminance of 700 candela/square meter (cd/m ² ) ), the measurement result was used to measure T ₉₅ by a service life measuring device (M6000) manufactured by Mc Science.

Table 6 shows the results of measuring the driving voltage, luminous efficiency, color coordinate (CIE) and service life (T ₉₅ . unit: time (h)) of the blue organic light emitting device manufactured according to the present invention. [Table 6] compound Driving voltage (V) Luminous efficiency (cd/A) CIE (x, y) Service life (T ₉₅ ) Example 1 2 4.20 6.60 (0.134, 0.100) 53 Example 2 11 4.16 6.64 (0.134, 0.100) 49 Example 3 60 4.43 6.69 (0.134, 0.100) 47 Example 4 114 4.35 6.70 (0.134, 0.101) 48 Example 5 115 4.24 6.68 (0.134, 0.101) 50 Example 6 155 4.22 6.73 (0.134, 0.100) 49 Example 7 235 4.23 6.70 (0.134, 0.100) 49 Example 8 351 4.10 6.68 (0.134, 0.100) 50 Example 9 382 4.18 6.60 (0.134, 0.100) 53 Example 10 383 4.19 6.81 (0.134, 0.101) 49 Example 11 386 4.23 6.70 (0.134, 0.100) 52 Example 12 387 4.35 6.70 (0.134, 0.101) 48 Example 13 406 4.16 6.64 (0.134, 0.100) 49 Example 14 418 4.20 6.60 (0.134, 0.100) 53 Example 15 438 4.20 6.60 (0.134, 0.100) 53 Example 16 489 4.35 6.70 (0.134, 0.101) 48 Example 17 518 4.65 6.96 (0.134, 0.101) 50 Example 18 524 4.17 6.85 (0.134, 0.101) 51 Example 19 527 4.23 6.76 (0.134, 0.101) 49 Example 20 529 4.59 6.54 (0.134, 0.101) 45 Example 21 531 4.36 6.31 (0.134, 0.101) 47 Comparative example 1 NPB 5.16 6.00 (0.134, 0.101) twenty one Comparative example 2 HT1 5.19 6.08 (0.134, 0.101) 20 Comparative example 3 HT2 5.20 6.04 (0.134, 0.101) 18 Comparative example 4 HT3 5.20 6.02 (0.134, 0.101) twenty three Comparative Example 5 HT4 5.20 6.05 (0.134, 0.101) twenty four Comparative Example 6 HT5 5.20 6.03 (0.134, 0.101) twenty two Comparative Example 7 HT6 5.20 6.05 (0.134, 0.101) 25

As can be seen from the results in Table 6, the organic light emitting device using the hole transport layer material of the blue organic light emitting device of the present invention had a low driving voltage and significantly improved luminous efficiency and service life compared to the comparative example.

Specifically, for the compounds of the present invention, it can be confirmed that when amine derivatives are used as the hole transport layer, the non-shared electron pairs of the amine can enhance the flow of holes and improve the hole transfer capacity of the hole transport layer, and the amine Partial combination with substituents with hole-enhancing properties also enhances the planarity and glass transition temperature of the amine derivatives to enhance the thermal stability of the compounds.

In addition, since the bandgap and energy level values of the triplet state (T1 value) are adjusted to improve the hole transfer capacity and improve the stability of molecules, it can be confirmed that the driving voltage of the device is reduced, the light efficiency of the device is improved, and the use of the device The lifetime characteristics are improved by the thermal stability of the compound.

Specifically, it can be confirmed that when the compound represented by Chemical Formula 1 of the present application has two substituents at one phenyl group of the naphthobenzofuran core (that is, one or more aryl groups are substituted Amino groups and aryl groups, or one or more aryl groups substituted by amine groups and heteroaryl groups containing O or S) when used in the hole transport layer, the luminous efficiency and service life are excellent, because the amine group The substituted aryl group in delocalizes the highest occupied molecular orbital (HOMO) energy level of the compound to stabilize the HOMO energy of the compound. ( 1 ) Manufacture of organic light-emitting devices Comparative Example 8 to Comparative Example 14 and Example 22 to Example 42

The glass substrate (in which ITO was thinly coated to have a thickness of 1,500 Å) was ultrasonically washed with distilled water. When washing with distilled water is complete, the glass substrate is ultrasonically washed with a solvent such as acetone, methanol, and isopropanol, dried and then UVO-treated using UV in a UV cleaner for 5 minutes. Thereafter, the substrate was transferred to a plasma washer (PT), and then plasma-treated in a vacuum state for ITO work function and in order to remove residual films, and transferred to a thermal deposition apparatus for organic deposition.

Subsequently, the air in the chamber was evacuated until the vacuum degree in the chamber reached 10 ^-6 Torr, and then a hole injection layer with a thickness of 600 angstroms was deposited on the ITO by applying current to the cell to evaporate 2-TNATA on the substrate.

By placing the following N,N'-bis(α-naphthyl)-N,N'-diphenyl-4,4'-diamine (NPB) in another cell in the vacuum deposition apparatus and applying current To the cell to evaporate the NPB, deposit a hole transport layer with a thickness of 300 Å on top of the hole injection layer.

Thereafter, an underlayer was formed by depositing compounds shown in Table 7 below to 100 angstroms.

Compound HT1 to Compound HT6 in Table 7 below are as follows.

The light-emitting layer is thermally vacuum-deposited thereon as follows. The emissive layer was deposited by adding 9-[4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl]-9'-phenyl-3,3'- A compound of bis- 9H -carbazole was deposited to 400 Å as the host, and the deposited layer was doped to 7% of the thickness of the light-emitting layer with Ir(ppy) ₃ as the green phosphorescent dopant. Thereafter, BCP as a hole blocking layer was deposited to have a thickness of 60 Å, and Alq ₃ as an electron transport layer was deposited thereon to have a thickness of 200 Å.

Finally, an electron injection layer was formed by depositing lithium fluoride (LiF) to have a thickness of 10 angstroms on the electron transport layer, and then an aluminum (Al) negative electrode was deposited to have a thickness of 1,200 angstroms on the electron injection layer to A negative electrode is formed to fabricate an organic light emitting device.

Meanwhile, all organic compounds required for manufacturing an organic light emitting device were subjected to vacuum sublimation purification at 10 ⁻⁸ Torr to 10 ⁻⁶ Torr for each material, and used for manufacturing an organic light emitting device. ( 2 ) Evaluation of organic light-emitting devices

For the organic light-emitting devices of Comparative Example 8 to Comparative Example 14 and Example 22 to Example 42 manufactured as above, the electroluminescent light emission (EL) characteristics were measured using M7000 manufactured by Mc Science, and using the measurement results, using the M7000 manufactured by Mc Science The service life measurement device (M6000) manufactured by the company is used to measure the service life T ₉₀ (unit: h, hour) (which is the time until the luminance becomes 90% compared to the initial luminance when the reference luminance is 6,000 cd/m²) , and the measurement results are shown in Table 7 below. [Table 7] compound Driving voltage (V) Luminous efficiency (cd/A) Service life (T ₉₅ ) Example 22 2 4.30 6.80 250 Example 23 11 4.25 6.85 250 Example 24 60 4.29 6.90 220 Example 25 114 4.29 6.87 253 Example 26 115 4.30 6.86 253 Example 27 155 4.29 6.88 243 Example 28 235 4.31 6.90 248 Example 29 351 4.27 6.91 250 Example 30 382 4.29 6.87 251 Example 31 383 4.31 6.88 248 Example 32 386 4.32 6.92 256 Example 33 387 4.30 6.92 249 Example 34 406 4.23 6.93 253 Example 35 418 4.28 6.85 252 Example 36 438 4.29 6.87 252 Example 37 489 4.27 6.85 262 Example 38 518 4.19 6.93 275 Example 39 524 4.36 6.92 285 Example 40 527 4.68 6.82 243 Example 41 529 4.52 6.86 265 Example 42 531 4.32 6.88 255 Comparative Example 8 NPB 5.32 6.18 172 Comparative Example 9 HT1 5.36 6.14 171 Comparative Example 10 HT2 5.30 6.18 182 Comparative Example 11 HT3 5.33 6.16 167 Comparative Example 12 HT4 5.30 6.10 178 Comparative Example 13 HT5 5.20 6.22 168 Comparative Example 14 HT6 5.19 6.22 149

From the results in Table 7, it can be confirmed that during the formation of the hole transport auxiliary layer, in the case of using the organic light-emitting devices according to Examples 22 to 42 of the compound of the present application, by having naphthobenzofuran contained therein, The substituted structure of the two specific substituents of the amine group effectively prevents electrons from passing through opposite sides of the electron transport layer to delocalize the highest occupied molecular orbital (HOMO) energy level, thereby stabilizing the HOMO energy, and thus, During the formation of the hole transport auxiliary layer, its luminous efficiency and service life were better than those of the organic light emitting devices of Comparative Example 8 to Comparative Example 14 that did not use the compound according to the present application.

Specifically, it can be confirmed that the amine group and specific aryl groups (such as fluorenyl and pyrenyl) in naphthobenzofuran and aryl or heteroaryl groups consisting of 21 to 60 carbon atoms can be obtained by having substituents among them The double-substituted structure effectively prevents electrons from passing through the opposite side of the electron transport layer to delocalize the highest occupied molecular orbital (HOMO) energy level, thereby stabilizing the HOMO energy, and therefore, its luminous efficiency during the formation of the bottom layer The luminous efficiency and service life of the organic light-emitting device of the comparative example not using the compound according to the present application are better than those of the organic light-emitting device according to the present application.

100: Substrate 200: positive electrode 300: organic material layer 301: Hole injection layer 302: Hole transport layer 303: luminescent layer 304: Hole blocking layer 305: electron transport layer 306: Electron injection layer 400: negative electrode

1 to 3 each schematically illustrate a stack structure of an organic light emitting device according to an exemplary embodiment of the present application.

100: Substrate

200: positive electrode

300: organic material layer

400: negative electrode

Claims (10)

A heterocyclic compound represented by the following chemical formula 1: [chemical formula 1]

Wherein, in Chemical Formula 1, L1 and L2 are the same or different from each other, and are each independently a direct bond, a substituted or unsubstituted arylylene group having 6 to 60 carbon atoms, or a arylylene group having 2 to 60 carbon atoms A substituted or unsubstituted heteroarylylene group of atoms, a and b are each an integer from 0 to 3, when a is 2 or higher than 2, L1 in parentheses are the same or different from each other, and when b is 2 or When it is higher than 2, L2 in parentheses are the same or different from each other, one of R1 and R2 is a substituted or unsubstituted amino group, and the other is unsubstituted or via deuterium, has 1 to 10 carbon atoms fluorenyl substituted with one or more substituents selected from the group consisting of alkyl and aryl having 6 to 20 carbon atoms; substituted or unsubstituted pyrenyl; having 21 to 60 A substituted or unsubstituted aryl group of carbon atoms; or a substituted or unsubstituted heteroaryl group with 2 to 60 carbon atoms, X1 and X2 are each independently hydrogen, deuterium, halogen group, with A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms, a substituted or unsubstituted cycloalkyl group having 6 to 60 carbon atoms Unsubstituted aryl or substituted or unsubstituted heterocyclic group having 2 to 60 carbon atoms, m is an integer from 0 to 3, and when m is 2 or higher than 2, X1 in parentheses are the same or different from each other, and n is an integer from 0 to 5, and when n is 2 or higher, X2 in parentheses are the same or different from each other. The heterocyclic compound as described in Claim 1, wherein Chemical Formula 1 is represented by the following Chemical Formula 2 or Chemical Formula 3: [Chemical Formula 2]

[chemical formula 3]

In Chemical Formula 2 and Chemical Formula 3, the definitions of L1, L2, R1, R2, X1, X2, a, b, m, and n are the same as those in Chemical Formula 1, and L3 to L6 are each independently a direct bond or have 6 A substituted or unsubstituted aryl group of up to 60 carbon atoms, c to f are each an integer of 0 to 3, and when c to f are each 2 or higher than 2, the substituents in the brackets are the same as each other or different, and R3 to R6 are each independently substituted or unsubstituted aryl having 6 to 60 carbon atoms, substituted or unsubstituted heteroaryl having 2 to 60 carbon atoms. The heterocyclic compound as claimed in claim 2, wherein R3 to R6 are each independently a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, a substituted or unsubstituted aryl group having 2 to 40 carbon atoms Unsubstituted heteroaryl. The heterocyclic compound as claimed in item 1, wherein the deuterium content of the heterocyclic compound represented by Chemical Formula 1 is 10% to 100%. The heterocyclic compound as claimed in claim 1, wherein X1 and X2 are each independently hydrogen or deuterium. The heterocyclic compound as claimed in item 1, wherein chemical formula 1 is represented by any one of the following compounds:

. An organic light-emitting device, comprising a first electrode, a second electrode, and an organic material layer having one or more layers disposed between the first electrode and the second electrode, wherein one or more of the organic material layers The plurality of layers includes the heterocyclic compound as claimed in any one of claims 1 to 6. The organic light-emitting device according to claim 7, wherein the organic material layer includes a hole transport layer having one or more layers, and the hole transport layer includes the heterocyclic compound. The organic light-emitting device according to claim 7, wherein the organic material layer includes a hole transport auxiliary layer having one or more layers, and the hole transport auxiliary layer includes the heterocyclic compound. The organic light-emitting device according to claim 7, further comprising one or two or more than two layers selected from the group consisting of: light-emitting layer, hole injection layer, hole transport layer, electron injection layer, Electron transport layer, hole auxiliary layer and hole blocking layer.

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